The aim of the following proposal is the development of the regio- and enantiospecific rhodium-catalyzed allylic substitution as a general cross-coupling reaction, and the combination with free radical cyclization and novel metal-catalyzed carbocyclization reactions. It is anticipated that these processes will facilitate the design and application of novel strategies that permit the expeditious total synthesis of the biological important molecules. The specific areas of interest are summarized as follows: New Allylic Amination Reactions with Cyclic Vinylogous Amides and Ureas: the development of new allylic amination reactions with vinylogous amides and ureas for the total synthesis of the alkaloids, lepadiformine and batzelladine D. New Metal-Catalyzed Carbocyclization Reactions: enantioselective metal-catalyzed [2+2+2] carbocyclization reactions using chiral rhodium complexes, and the combination with allylic substitutions for new tandem processes. The development of a temporary silicon-tethered (TST) rhodium-catalyzed [4+2+2] carbocyclization approach to the diterpene, epoxydictymene.